The present invention relates generally to coagulants for water treatment applications. In general, coagulants are utilized to remove suspended solid particles from aqueous systems.

Coagulants typically fall into the general category of inorganic (trivalent, divalent metal salts) or organic (water soluble polyelectrolytes). Examples of widely used inorganic coagulants are aluminum sulfate Al₂(SO₄)₃, aluminum chloride AlCl₃, aluminum chlorohydrate Al₂(OH)₅Cl, ferric chloride FeCl₃, ferric sulfate Fe₂(SO₄)₃, and calcium chloride. Examples of commonly used water soluble or solution polyelectrolytes are p-DMDAAC (polydimethyl diallyl ammonium chloride) and Epi-DMA polyamine.

Many inorganic coagulants are compatible with solution cationic polyelectrolytes and can be combined to form stable combinations. In recent years, many different blend formulations of an inorganic coagulant with a high charge solution cationic polyelectrolyte have been patented and marketed. An example of an inorganic coagulant/polymer blend might be: 5 parts of a standard 28° Baumé AlCl₃ solution mixed with 1 part of Epi-DMA polyamine. More examples, limits, and ranges are explained in United States Patent Nos. 4,746,457 , 4,800,039 , and 5,035,808 to Calgon Corporation, and further in United States Patent Nos. 2,862,880 , 3,285,849 , 3,472,767 , 3,489,681 , 3,617,569 , 4,137;165 , 4,450,092 , 4,582,627 , 4,610,801 , and 4,655,934 , the disclosures of which are incorporated herein by reference in their entirety. Normally, these compositions are physical blends of an inorganic trivalent metal salt solution and a water soluble polymer solution, which is a simple mixture of the components where both components retain their original identity or chemical composition, but provide utility and advantages such as:

1. 1. a synergy of adding the inorganic and polymeric coagulants simultaneously as a blend; and
2. 2. ease of use - using one product instead of two (thereby eliminating feed systems, equipment, and handling).

Wastewater treatment systems typically require the use of trivalent metal salts, a polymer or a combination of both in the coagulation process. Both ferric coagulants such as FeCl₃ blends and aluminum coagulants such as alum or Al₂(OH)₅Cl blends are often used for these processes. Both the ferric and aluminum coagulants provide different desirable properties. However, these coagulants are normally incompatible with each other.

It was thus desired in the art to develop a single coagulant which would combine the desirable properties of ferric and aluminum coagulants.

According to a first aspect of invention there is provided a composition as claimed in claim 1. According to a second aspect of the invention there is provided a process as claimed in claim 8.

Further embodiments of the invention are included in the dependent claims.

The present invention comprises a composition that is the reaction product of a trivalent metal salt, excluding chromium salts, an acid phosphorous compound and an aluminum hydroxy chloride, and a process for preparing the same.

The method of use according to the present invention comprises adding this reaction product in an effective amount to the solution to be treated. The composition of the present invention is an excellent and unique coagulant for most water treatment applications.

As used herein, the phrase "effective amount" refers to that amount of the claimed reaction product which is helpful to at least partially treat (coagulate) the impurities in the wastewater or system being treated.

The above composition will become more apparent when reference is made to the following detailed description, taken in conjunction with the appended figures, in which:

• FIG. 1 is an Al-27 NMR spectrum of monoaluminum phosphate;
• FIG. 2 is an Al-27 NMR spectrum of aluminum chlorohydrate; and
• FIG. 3 is an Al-27 NMR spectrum of the reaction mixture of iron(III) chloride, monoaluminum phosphate and aluminum chlorohydrate.

These figures are discussed in detail below.

The present invention was discovered when the inventors were attempting to obtain the desirable properties of FeCl₃ blends and Al(OH)₅Cl blends by mixing these two inorganics and then combining the resultant mixture with a cationic polyelectolyte and other ingredients. However, they discovered that mixtures of trivalent metal salts such as FeCl₃ and aluminum hydroxy chlorides such as Al₂(OH)₅Cl are incompatible and all attempts to combine such mixtures ended in a gelled/solidified reaction product which was not usable.

It was unexpectedly discovered that FeC'₃ solution and Al₂(OH)₅Cl solution can be stabilized and combined through the use of a third ingredient, monoaluminum phosphate. The inventors have discovered a method of combining these previously incompatible coagulants and creating a stable, complex ion coordination compound that exhibits increased efficacy as a coagulant for industrial and municipal water treatment.

A composition, and process for preparing the same, has been discovered by the inventors comprising the reaction product of a trivalent metal salt other than chrominum salts, an aluminum hydroxy chloride, and an acid phosphorous compound which acts as a stabilizing compound.

The preferred process of preparing the present invention is the addition of the acid phosphorous compound (stabilizer) to the trivalent metal salt, soon followed by the addition of the aluminum hydroxy chloride. A small exotherm results from the addition of the acid phosphorous compound (stabilizer) to the trivalent metal salt. A larger and more vigorous exotherm results from the subsequent addition of the aluminum hydroxy chloride. Based upon this exotherm, as well as color changes and partial precipitation (and re-dissolution), it is believed that the components are reacting and a new compound is formed. Although the order of addition of these compounds to form the new compound may be altered, the above order of addition is preferred. If the trivalent metal salt and the aluminum hydroxy chloride are combined without the acid phosphorous compound, a slurry will be formed which will generally solidify in less than an hour. In order to create a stable final product, if this order of addition is utilized, the acid phosphorous compound should be added to this mixture prior to solidification, or preferably within 40 minutes. However, reconstitution after solidification is possible by the addition of the acid phosphorous compound. The least preferred order of addition is when the acid phosphorous compound is alone first mixed with the aluminum hydroxy chloride, because a solid mass will be formed almost instantaneously. However, this solid mass can be reconstituted by the addition of FeCl₃. For these reasons, the above noted order of addition is preferred.

This new resultant compound is stable and appears to be different in composition from the compounds used in the preparation process. The conclusion that a new compound is formed is supported by Figures 1-3 which illustrate Al-27 NMR spectra for a compound formed from the reaction of the volume formula 10 FeCl₃ (about 40% active raw material in water), 3 monoaluminum phosphate (Al(H₂PO₄)₃ • XH₂O) (about 50 wt% in water), and 5 Al(OH)₅Cl (about 50 wt% in water). Commerciably available FeCl₃ solution is 38 to 42% active raw material in water. Commercially available monoaluminum phosphate and Al(OH)₅Cl are both 50 wt% in water, plus or minus 1 to 2%.

The combination of a peak's shape and position yield structural information in NMR spectroscopy. The position is based upon a relative marker to a selected standard material and is measured in ppm shifts in frequency. The standard reference material used in these spectra was aluminum oxide (Al₂O₃) at 0 ppm. The shape of the peak (singlet, doublet, etc.) is dependent upon the nuclei's interaction with neighboring atoms. The combination of peak position and shape is a function of the nuclei's environment, and thus, its structure.

Figure 1 is an Al-27 NMR spectrum of monoaluminum phosphate. This spectrum shows a single band centered at ca. - 77.7 ppm relative to the standard. The width of the peak is indicative of the structure in solution.

Figure 2 is an Al-27 NMR spectrum of aluminum chlorohydrate (Al₂(OH)₅Cl). This spectrum shows a very broad set of peaks centered at ca. -57.8 and -68.6 ppm with the former peak being the much stronger band. This spectrum shows two peaks which are overlapped. There are also two significantly smaller peaks on either side of these two major bands which are probably minor impurities. This material is known to be polymeric in nature. In general, the higher the molecular weight of a material the more broad the peaks become.

Figure 3 is an Al-27 NMR spectrum of the reaction mixture of the present invention. This spectrum shows the product of the claimed reaction mixture of iron(III) chloride, monoaluminum phosphate and aluminum chlorohydrate according to the current reaction, using the concentrations and parts per volume of these three compounds in the preferred embodiment. In Figure 3, the aluminum NMR peak is a very much sharper singlet and is shifted to a position at ca. -26.2 ppm relative to the standard. These changes indicate that a reaction has taken place, that the two component raw materials (iron(III) chloride and aluminum chlorohydrate) are most likely limiting reagents in this reaction, and that the structure of the final product is simpler than the aluminum chlorohydrate precursor. The aluminum exists in a single type of chemical environment, hence the rationale for the proposed structure of a new compound.

The molecular formula of this preferred embodiment, which is the subject of Figure 3 is:



        Iron (III) salt of [Al_n(OH)_a(H₂PO₄)_b(Cl)_c(H₂O)_d]^3n-a-b-c where a+b+c>3n

This new composition is the product of a Lewis/Acid Base type reaction in which a stable, complex ion coordination compound is formed as follows:

A+B → "intermediate" (4° C. temperature rise observed)

"intermediate" + C → new compound (20° C. temperature rise observed) where: (% Active Basis) A= Iron Chloride 17.5% - 20% B= Phosphoric Acid, Aluminum Salt (3:1) 8% - 10% C= Aluminum Chloride, Basic 11.0% - 13%

A typical structure of this new compound of the preferred embodiment is represented below where the H₂O, Cl, OH and H₂PO₄ ligands can vary in number, as well as in their position on the metal ion in the coordination complex. The nature of the bond between each ligand and the central metal atom is coordinate covalent.

The preferred embodiment of the present invention composition, by volume, is:

10

FeCl₃ (aqueous solution about 40% active raw material in water)

3

Monoaluminum phosphate (Al(H₂PO₄)₃ • XH₂O) (about 50 wt% in water)

5

Al₂(OH)₅Cl (about 50 wt% in water)

1

CaCl₂ (30% solution)

2

Ca-250 (Epi-DMA polyamine) (50 wt% in water)

Multiple experiments involving the modification of the volume of the above ingredients in the preferred embodiment have been performed. It has been determined that although the above noted volumes provide the preferred combination, these ratios may be altered while still maintaining a stable reaction product and the desired coagulation properties to varying degrees. It has been determined that (using the concentrations set forth above) the volume of the FeCl₃ component may be varied from 3 to 30 parts, the monoaluminum phosphate may be varied from .5 to 10 parts, and the Al₂(OH)₅Cl may be increased to as high as 20 parts. However, the upper limit of the Al₂(OH)₅Cl volume appears to be 20 because precipitation begins to occur at this level. Although the quality of the resultant compounds varied proportionally with the deviation from the preferred embodiment, the resultant compounds provided stable reaction products. Further tests have performed varying the combinations of different trivalent metal salts, acid phosphorous compounds and aluminum hydroxy chlorides, as well as the volumes of each such component. The Example below demonstrates the results of selected tests on volume and component variations.

The volumetric ratios set forth above for components of the preferred embodiment are also applicable to the various claimed combinations of the other trivalent metal salts, acid phosphorous compounds and aluminum hydroxy chlorides. It is known by one skilled in the art that these various compounds can be obtained in varying concentrations. In order to obtain the most preferred ratio of components of various substitute components of varying concentration, one must obtain the same ratio of molar amounts of ferric, phosphate or phosphite and aluminum as that of the preferred embodiment above. For example, phosphoric acid is commercially available in about 85 wt% in water as compared to about 50 wt% of monoaluminum phosphate. Thus a component of different concentration can be used if the correct molar ratio is obtained.

It appears that the calcium chloride and CA-250 components are present only as a physical blend with the compound which is the result of the reaction. The resulting blend of the reaction product and the CaCl₂ and CA-250 (Epi-DMA polyamine) is a "sweep-floc" which functions as a coagulant and a flocculent and, as noted above, could be useful in many water treatment processes. Other standard additives can also be mixed with the reaction product.

In place of the CA-250 (Epi-DMA polyamine), p-DMDAAC may be utilized under certain circumstances in the physical blend with the subject reaction product. The p-DMDAAC may be utilized when the trivalent metal salt FeCl₃ (in the preferred embodiment) is diluted by 10 to 40% with water prior to the addition of the acid phosphorous compound and the aluminum hydroxy chloride. In order to utilize p-DMDAAC with the already prepared reaction product of the preferred embodiment, the entire reaction product must be diluted by 10 to 40% with water prior to the addition of p-DMDAAC. If phosphoric acid is substituted for the monoaluminum phosphate of the preferred embodiment, dilution of either FeCl₃ or the entire reaction product should be by 10 to 80% with water, otherwise precipitation will occur.

Tests have also been performed involving the variance of the amounts of CaCl₂ and the amount of the CA-250 (Epi-DMA polyamine). The volumes of these compounds have been varied both together and on an independent basis. The variance of these two components appears to have a negligible effect on the formulation.

As noted above, although the preferred embodiment utilizes FeCl₃ as the trivalent metal salt, monoaluminum phosphate as the acid phosphorous compound, and Al₂(OH)₅Cl as the aluminum hydroxy chloride, substitutions may be made for each of these compounds while still resulting in a stable, effective reaction product.

The preferred trivalent metal salts are those of Group 8. The more preferred trivalent metal salts are metal halides. However, the most preferred trivalent metal salts are ferric, such as FeCl₃, Fe₂(SO₄)₃, FeBr₃ and Fe (NO₃)₃. Additionally, blends of the foregoing may be utilized. Ferric halide is more preferred, while ferric chloride is most preferred. The preferred anions of the salt are chloride and halide. Sulfate is a less preferred anion of the salt. Nitrate may also be employed as an anion for the salt.

The preferred acid phosphorous compounds of the present invention are selected from the group consisting of acid phosphites (including phosphorous acid), acid phosphates (including phosphoric acid), and phosphonic acid. Acid phosphorous compounds having the following formula may be utilized:



        M_nH_xPO_q

• Where: M = cation such as a metal or ammonium
• n = 0 to 2
• x = 1 to 3
• q = 3 or 4

The aluminum hydroxy chloride compounds which may be used in the formulation of the composition of the present invention are those of the general formula Al₂(OH)_yCl_z, where y= 0.1 to 5 and z= 1 to 5.9 The more preferred are those where y= 1 to 5 and z= 1 to 5. The most preferred are those where y= 1.8 to 5 and z= 1 to 4.2.

In preparing the claimed reaction product, AlCl₃ can be utilized as the trivalent metal salt and combined with Al₂(OH)₅Cl and a stabilizer (acid phosphorous compound). An exotherm will occur and a reaction product will be formed. AlCl₃ can also be utilized as a substitute for the aluminum hydroxy chloride component and combined with FeCl₃ and a stabilizer. However, in this circumstance, a reaction product is not formed and a blend is achieved. Nevertheless, this blend exhibits good coagulation properties.

Experiments have also been performed where the CaCl₂ compound has been substituted with MgCl₂ and BaCl₂ without resulting serious detriment to the performance of the resultant mixture with the reaction product. The CA-250 (Epi-DMA polyamine) may also be substituted with other Epi-DMA polyamines. CA-250 is preferred because of its relative low to medium molecular weight. CA-250 is a commercial polyamine product sold by Calgon Corporation.

This resultant new compound has been demonstrated to be an excellent and unique coagulant for most water treatment applications including E-coat waste treatment, water-borne paint waste coagulation, oily waste and solvent-borne paint detackification. It is also exhibits utility in general wastewater treatment, municipal wastewater treatment, metals removal from water, paper making waste water, water containing chemical compounds, water containing organic compounds, water containing biological compounds, poultry processing waste, ink containing solutions, raw water clarification (such as municipal drinking water and industrial purification), oil/water separation, water containing suspended solids, color removal (colored solutions), waste clay slurry, coal waste, mineral processing water, oily waste, water containing suspended solids, water containing paint solids and others. The resultant new compound has also been demonstrated to remove metals from water, including heavy metals such as lead and nickel. E-coat waste is the wastewater generated from electrolytic primer coating.

The method of using the new compound for coagulation in these various systems consists of adding the new compound to the system in an effective amount.

This new compound also may be utilized for enhanced coagulation. Enhanced coagulation is the reduction of total organic contaminants (TOC). The reduction of organic contaminants in drinking water is desirable to minimize formation of chlorinated hydrocarbons formed during the chlorination process.

The most preferred method for producing the claimed reaction product entails the following steps:

1. 1. At ambient temperature, add 3 parts by volume monoaluminum phosphate solution (about 50 wt% in water) to 10 parts by volume FeCl₃ aqueous solution (about 40% active raw material in water). During the addition of the monoaluminum phosphate solution to the FeCl₃ solution, some reaction will take place. There may be some partial precipitations and color changes - and striations in the solutions. However, when the reaction is complete, everything is in solution and it appears stable.
2. 2. Next, the 5 parts by volume aluminum chlorohydrate solution (about 50 wt% in water) is added to the mixture of FeCl₃ and monoaluminum phosphate (and further reaction takes place). The resultant solution goes through a violent exotherm. The solution becomes hot, and the solution becomes homogeneous. When the solution cools down, it remains compatible and homogeneous.
3. 3. Preferably, 1 part by volume CaCl₂ (30% solution) and 2 parts per volume of a polymer, such as CA-250 (Epi-DMA polyamine 50 wt%) are then added. The CaCl₂ is added for hardness and the polymer to enhance coagulation and to begin flocculation (to help form the pin floc). There appears to be no further reaction when the CaCl₂ and the polymer are added.

As noted above, it will be apparent to one skilled in the art that this process may be duplicated utilizing the other trivalent metal salts, acid phosphorous compounds, and aluminum hydroxy chlorides herein claimed, if the same noted molar ratios are utilized.

The following example is included to further describe and demonstrate the invention in greater detail. This example is not intended to limit the scope of the invention in any way. This example, and the tables included therein, demonstrate the performance of the claimed invention, including the preferred embodiment and other claimed reaction products formed from various Group 8 trivalent metal salts, acid phosphorous compounds and aluminum hydroxy chloride components, on the treatment of E-coat waste. Also included are entries illustrating the effectiveness of treating E-coat waste with only a trivalent metal salt and only an aluminum hydroxy compound.

The following test procedure was used to compile the results contained in the following tables.

1. 1. 2.5 gms of the selected coagulant and/or reaction product was weighed and placed into a B-cup.
2. 2. 7.5 gms of deionized water was placed into the same B-cup and mixed until uniform.

1. 1. 495 mls of deionized water was added to a glass jar (a graduated cylinder was used).
2. 2. The glass jar was placed on a gang stirrer and mixed at 100 rpm.
3. 3. 5 mls of neat E-coat waste was added to the water.
4. 4. 0.6 mls of the selected coagulant and/or reaction product solution (300 ppm) was added to the glass jar.
5. 5. The solution was mixed at 100 rpm for 15 seconds.
6. 6. The pH was lowered to 2.9 using stock H₂SO₄ (10 gm H₂SO₄ + 190 gm DiH₂O).
7. 7. The number of drops of stock H₂SO₄ used to lower the pH was recorded.
8. 8. The solution was mixed at 100 rpm for 15 seconds.
9. 9. The pH was increased to 8.5 using a soda ash solution (20 gm soda ash + 80 gm DiH₂O).
10. 10. The number of drops of soda ash solution used to increase the pH was recorded.
11. 11. The solution was mixed at 100 rpm for 15 seconds.
12. 12. 2 mls of flocculent - Pol EZ 8736 or Pol EZ 7736 [0.5% product] which are commercially available high molecular weight polymers sold by Calgon Corporation - was placed in a syringe and added by the following method:
    1. a) the tip of the syringe was placed below the surface of the solution at approximately the top of the vortex;
    2. b) the flocculent was added and timed for exactly 10 seconds;
    3. c) after the ten second period ended, the agitation was turned down to 50-60 rpm;
    4. d) the floc was allowed to develop for 30 seconds; and
    5. e) the agitation was then turned off.
13. 13. The floc was then allowed to settle for 10 minutes.
14. 14. The floc size and the appearance of the solution was then recorded (visual inspection only).
15. 15. 20 mls of the solution was removed with a syringe for a turbidity reading.
16. 16. The turbidity reading in NTU (nephelometric turbidity units) was recorded.
17. 17. The agitation was then turned on and the motion speed was slowly increased to ≤ 50 rpm.
18. 18. The solution was mixed for 30 seconds and the percentage of detackification was recorded.
19. 19. The motor speed was then increased to 100 rpm and the solution was mixed for 30 seconds.
20. 20. The percentage of detackification was then recorded (if detackification of 100% was recorded at 50 rpm, no reading was necessary at 100 rpm and therefore was not taken).

Unless otherwise noted, this procedure was utilized to obtain the results set forth in the tables below. Flocculation refers to the settling of suspended solid particles in the solution. Turbidity as used herein is defined as the cloudiness of the solution casued by suspended particles.

This table illustrates the performance of the preferred embodiment, 10 FeCl₃, 3 (Al(H₂PO₄)₃ • XH₂O) and 5 Al₂(OH)₅Cl, 1 CaCl₂ and 2 Ca-250, in the concentrations set forth above, as 3930-93. In 3982-84A, the (Al(H₂PO₄)₃ • XH₂O) was substituted with HEDP in the same molar ratio. In 3982-86A and 3982-87, the (Al(H₂PO₄)₃ • XH₂O) has been likewise substituted with vinyl phosphonic acid and dimethyl phosphite, respectively. 3930-93 3982-84A 3982-86A 3982-87 Description Preferred embodiment HEDP Vinyl Phosphonic acid Dimethyl Phosphite Product Dilution 7.5 gms/ 7.5gms/ 7.5gms/ 7.5gms/ (Deionized water/product) 2.5 gms 2.5 gms 2.5 gms 2.5 gms Appearance medium amber med-dk amber yellow very pale blue Use Concentration 0.60mls/ 0.60mls/ 0.60mls/ 0.60mls/ (mls/ppm) 300ppm 300ppm 300ppm 300ppm E-coat Composition 495mls/ 495mls/ 495mls/ 495mls/ 5mls 5mls 5mls 5mls pH to 2.9 30 drops 29 drops 34 drops 31 drops pH to 8.5 45 drops 50 drops 52 drops 40 drops Floc size/appearance large/hazy med fluffy/ large/lt. haze med-lg/sl haze sl haze Turbidity 93.3 54.2 39.6 72.4 Detackification good fair fair-good bad 50 rpm: 100% 50& 65% 0% 100 rpm: 100% 100% 60%

This table likewise illustrates how the performance of the preferred embodiment is effected by changes in the type and amount of the acid phosphorous compound utilized. The composition of the preferred embodiment remained constant for each trial, except: in 3982-79A, a lower volume of (Al(H₂PO₄)₃ XH₂O) ("MAP") was utilized; in 3982-79B, a lower volume of H₃P0₄ was substituted for the MAP; in 3982-79C, H₃PO₄ was substituted for the MAP in the same volume; and in 3982-80G, NaH₂P0₄ was substituted for the MAP in the same volume. 3930-93 3982-79A 3982-79B 3982-79C 3982-80A 3982-80G Description Preferred Embodiment Low MAP Low H₃PO₄ Std H₃PO₄ Std H₃PO₃ Std NAH₂PO₄ Product Dilution Deionized water/product 7.5gms/2.5gms 7.5gms/2.5gms 7.5gms/2.5gms 7.5gms/2.5gms 7.5gms/2.5gms 7.5gms/2.5gms Appearance good/med amber good/dk amber good/dk amber good/yellow good/dk amber good/dk amber Use Concentation (mls/ppm) 0.60mls/300ppm 0.60mls/300ppm 0.60mls/300ppm 0.60mls/300ppm 0.60mls/300ppm 0.60mls/300ppm E-coat Composition Deionized water/ e-coat waste 495mls/5mls 495mls/5mls 495mls/Smls 495mls/Smls 495mls/5mls 495mls/5mls pH to 2.9 27 drops 25 drops 24 drops 25 drops 23 drops 24 drops pH to 8.5 60 drops 60 drops 60 drops 60 drops 60 drops 60 drops Floc size/appearance very lg/sl haze lg.tight/very sl. haz very lg./hazy lg. loose/sl. haze med.loose/almost clear lg.loose/sl. haze Turbidity 90/88 67 72 68 31 44.7 Detackification Good Good Good Good Good Good 50 rpm: 90% 100% 100% 100% 90% 100% 100 rpm: 100% 100%

Tables 3 and 4 illustrate the effect of altering the use concentration of the preferred embodiment. The numbers included under the heading "Description" refer to the volumes 10 FeCl₃, 3 (Al(H₂PO₄)₃ • XH₂O), 5 Al₂(OH₅)Cl, 1 Cacl₂ and 2 Ca-250, of the component concentrations of each set forth above. #1 #2 #3 #4 #5 #6 Description Preferred Embodiment 10+3+5+1+2 Preferred Embodiment 10+3+5+1+2 Preferred Embodiment 10+3+5+1+2 Preferred Embodiment 10+3+5+1+2 Preferred Embodiment 10+3+5+1+2 Preferred Embodiment 10+3+5+1+2 Product Dilution Deionized water/ product 7.5gms/2.5 gms 7.59ms/2.5gms 7.59ms/2.5gms 7.5gms/2.5gms 7.5gms/2.5gms 7.5gms/2.5gms Appearance amber amber amber amber amber amber Use Concentation (mls/ppm) 0.0mls/ 0ppm 0.04mls/ 20ppm 0.10mls/50ppm 0.20mls/ 100ppm 1.00mls/500ppm 2.00mls/1000ppm E-coat Composition Deionized water/ e-coat waste 495mls/5ml s 495mls/5mls 495mls/5mls 495mls/5mls 495mls/5mls 495mls/5mls pH to 2.9 n/a n/a n/a n/a n/a n/a pH to 8.5 n/a n/a n/a n/a n/a n/a Floc size/appearance tacky tacky tacky tacky hard floc/clear spongy floc Turbidity 58.5 49.9 48.2 34.1 14.8 32.9 Detackification Bad Bad Bad Bad Good Good 100 rpm: 0% 0% 0% 0% 100% 100% #1 #2 #3 #4 #5 #6 Description Preferred Embodiment 10+3+5+1+2 Preferred Embodiment 10+3+5+1+2 Preferred Embodiment 10+3+5+1+2 Preferred Embodiment 10+3+5+1+2 Preferred Embodiment 10+3+5+1+2 Preferred Embodiment 10+3+5+1+2 Product Dilution Deionized water/product 7.5gms/2.5gms 7.5gms/2.5gms 7.5gms/2.5gms 7.5gms/2.5gms 7.5gma/2.5gms 7.5gms/2.5gms Appearance amber amber amber amber amber amber Use Concentation (mls/ppm) 0.40mls/200pp m 0.60mls/300ppm 0.80mls/400ppm 1.00mls/500ppm 1.20mls/600ppm 1.40mls/700ppm E-coat Composition Deionized water/ e-coat waste 495mls/5mls 495mls/Smls 495mls/5mls 495mls/5mls 495mls/5mls 495mls/5mls pH to 2.9 n/a n/a n/a n/a n/a n/a pH to 8.5 n/a n/a n/a n/a n/a n/a Floc size/appearance sl tacky sl tacky sl tacky fluffy fluffy fluffy Turbidity 80.6 62.1 63.9 41.6 39.0 39.9 Detackification Fair Good Good Good Good Good 50 rpm: > 50% 95% 100% 100% 100% 100%

Table 5 provides a comparative example of the testing of the preferred embodiment 3920-93, compared to the performance of the individual components thereof. Nos. 1 through 5 are demonstrative of the use of the individual component alone noted after the heading "Description". 3930-93 #1 #2 #3 #4 #5 Description Preferred Embodiment 40% FeCl,sol.. 50% MAP sol. 50% Al₂OH₅Cl sol. 30% CaCl₂ sol. 50% CA-250 sol. Product Dilution Deionized water/product 7.5gms/2.5gms 7.5gms/2.5gms 7.5gms/2.5gms 7.5gms/2.5gms 7.5gms/2.5gms 7.5gms/2.5gms Appearance med amber yellow water white/clear water white/clear water white/clear water white/clear Use Concentation (mls/ppm) 0.60mls/300ppm 0.60mls/300ppm 0.60mls/300ppm 0.60mls/300ppm 0.60mls/300ppm 0.60mls/300ppm E-coat Composition Deionized water/ e-coat waste 495mls/5mls 495mls/5mls 495mls/5mls 495mls/5mls 495mls/5mls 495mls/5mls pH to 2.9 41 drops 38 drops 44 drops 46 drops 50 drops 50 drops pH to 8.5 64 drops 64 drops 66 drops 68 drops 69 drops 70 drops Floc size/appearance lg-vig/slight haze extra lg/very hazy lg/hazy fine/very hazy very fine/turbid jelly/turbid Turbidity 76 146 138 181 275 296 Detackification Good Bad Very Bad 0% Fair None None 50 rpm: 100% 0% 20% 20% 0% 0% 100 rpm: 100% 40% 75% 0% 0%

Table 6 demonstrates the effect of varying the volume composition of components of the preferred embodiment and the effect of the complete omission of the Al₂OH₅Cl component. The ratios noted in this table utilize the concentrations of each component set forth above. #1 #2 #3 #4 #5 #6 Description Ratio (mls) FeCl₃ + MAP 10+3 FeCl, + MAP + Al₂OH₅Cl 10+3+5 Fe, + MAP + Al₂OH₅CL 15+3+5 Fe, + MAP + Al₂OH₅Cl 10+3+10 Fe, + MAP + Al₂OH₅Cl +CaCl₂ 10+3+5+1 Fe, + MAP + Al₂OH₅Cl + CaCl₂+CA250 10+3+5+1+2 Product Dilution Deionized water/product 7.5gms/2.5gms 7.5gms/2.5gms 7.5gms/2.5gms 7.5gms/2.5gms 7.5gms/2.5gms 7.5gms/2.5gms Appearance yellow amber amber very dark amber amber amber Use Concentation (mls/ppm) 0.60mls/300ppm 0.60mls/300ppm 0.60mls/300ppm 0.60mls/300ppm 0.60mls/300ppm 0.60mls/300ppm E-coat Composition Deionized water/ e-coat waste 495mls/5mls 495mls/5mls 495mls/5mls 495mls/5mls 495mls/5mls 495mls/5mls pH to 2.9 34 drops 38 drops 36 drops 40 drops 37 drops 37 drops pH to 8.5 60 drops 61 drops 63 drops 64 drops 61 drops 62 drops Floc size/appearance 1g. fluffy/hazy lg.sl.fluffy/ very hazy lg.fluffy/hazy 1g.fluffy/hazy large/hazy large/hazy Turbidity 144 95 103 139 99.3 80 Detackification Very bad Good Fair Bad Good Good 50 rpm: 0% 75% 50% 20% 100% 100% 100 rpm: 20% 95% 75% 50%

Table 7 sets forth the results of tests performed utilizing various aluminum hydroxy chlorides as substitutes for Al₂OH₅Cl in the preferred embodiment. These aluminum hydroxy chlorides are: Aluminum hydroxy chloride FORMULA % BASICITY % SOLIDS % Al₂O₃ A Preferred embodiemnt Al₂(OH)₅Cl 83 50 23.5 B Al₂(OH)₃Cl₂(SO₄)_0.5 50 30 10 C Al₂(OH)_1.8Cl_4.2 30 33 8 D Al₂(OH)₃Cl₂(SO₄)_0.5 70 50 15 E Al₂(OH)₃Cl₃ 50 33 10 F Ferrous Chloride (FeCl₂) - - 28 - - G Al₂(OH)₂Cl₄ 30 40 - - H Al₂(OH)₃Cl₃ 55 40 - - I Al₂(OH)₃SO₄SiO₃ -35 -35 - - Description Preferred Embodiment C D E H G B I F Product Dilution Deionized water/ product 7.Sgms/ 2.5gms 7.5gms/ 2.5gms 7.5gms/ 2.5gma 7.5gms/ 2.5gms 7.5gms/ 2.5gms 7.5gms/ 2.5gms 7.5gms/ 2.5gms 7.5gms/ 2.5gms 7.5gms/ 2.5gms Appearance It amber It amber It. amber yellow yellow yellow yellow yellow yellow Use Concentation (mls/ppm) 0.60mls/ 300ppm 0.60mls/ 300ppm 0.60mls/ 300ppm 0.60mls/ 300ppm 0.60mls/ 300ppm 0.60mls/ 300ppm 0.60mls/ 300ppm 0.60mls/ 300ppm 0.60mls/ 300ppm E-coat Composition Deionized water/ e-coat waste 495mls/ 5mls 495mls/ 5mls 495mls/ 5mls 495mls/ 5mls 495mls/ 5mls 495mls/ 5mls 495mls/ 5mls 495mls/ 5mls 49Smls/ 5mls pH to 2.9 46 drops 37 drops 41 drops 38 drops 39 drops 39 drops 38 drops 38 drops 35 drops pH to 8.5 105 drops 105 drops 131 drops 120 drops 106 drops 92 drops 100 drops 106 drops 106 drops Floc size/appearance 1g. fluffy/ clear 1g. fluffy/ sl haze 1g. fluffy/ sl haze 1g. fluffy/ sl haze 1g. fluffy/ sl haze 1g. fluffy/ sl haze 1g. fluffy/ sl haze 1g. fluffy/ sl haze 1g. fluffy/ sl haze Turbidity 18.5 35.7 29.0 34.9 52.4 35.3 33.4 36.6 53.9 Detackification good good good good fair-good fair-good fair-good good fair-good 50 rpm: 90%-95% 100% 90% 85%-90% 80-85% 80-85% 80-85% 85% 80-85% 100 rpm: 100% 100% 100% 100% 100% 100% 100% 100%

Table 8 illustrates the performance of the preferred embodiment compared to the performance when substitutions of various components are made in the same volume and concentration. The second column shows the effect of the substitution of FeBr₃ for FeCl₃. 4023-8A, 4023-8C and 4023-8E show the results of the substitution of the noted phosphorous compound for MAP. 4023-13A and 4023-13A show the results of the substitution of the noted component for CaCl₂. Description Preferred Embodiment FeBr₃ NH₄HPO₄ KH₂PO₄ Na₂ HPO₄ MgCl₂ BaCl₂ Product Dilution Deionized water/ product 7.5gms/ 2.5gms 7.5gms/ 2.5gms 7.5gms/ 2.5gms 7.5gms/ 2.5gms 7.5gms/ 2.5gms 7.5gms/ 2.5gms 7.5gms/ 2.5gms Appearance med lt amber very lt amber reddish dk reddish dk reddish med It amber med It amber Use Concentation (mls/ppm) 0.60mls/ 300ppm 0.60mls/ 300ppm 0.60mls / 300ppm 0.60mls/ 300ppm 0.60mls / 300ppm 0.60mls/ 300ppm 0.60mls/ 300ppm E-coat Composition Deionized water/ e-coat waste 495mls/ 5mls 495mls/ 5mls 495mls/ 5mls 495mls/ 5mls 495mls/ 5mls 495mls/ 5mls 495mls/ 5mls pH to 2.9 38 drops 31 drops 42 drops 40 drops 49 drops 40 drops 48 drops pH to 8.5 94 drops 28 drops 94 drops 103 drops 105 drops 92 drops 107 drops Floc size/appearance 1g. fluffy/ clear 1g. fluffy/ sl cloudy 1g. fluffy/ s1 haze 1g. fluffy/ hazy 1g. fluffy/ hazy med fluffy/ clear med fluffy/ hazy Turbidity 30 70 23.8 29.3 34.6 28.8 40.1 Detackification good good good fair fair good fair-good 50 rpm: 100 rpm: 80%

100% 85%

99% 90% 100% 50% 100% 75% 100% 90% 100% 80%

100%